Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li⁺ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano-vinylene-linked multipolar polymer framework namely CNF-COF, which can act as efficient ion sieves to modify solid polymer electrolytes to simultaneously tune Li migration and stable Li⁺ anodes for long-lifespan all-solid-state (ASS) Li metal batteries at high rate. The dual-decoration of cyano and fluorine groups in CNF-COF favorably regulates electronic structure via multipolar donor-acceptor electronic effects to afford proper energy band structure and abundant electron-rich sites for enhanced oxidative stability, facilitated ion-pair dissociation and suppressed anion movements. Thus, the CNF-COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders fast selective Li⁺ transport but also facilitates the Li dendrite suppression. Specifically, the constructed PEO composite electrolyte with an ultra-low CNF-COF content of only 0.5 wt % is endowed with a wide electrochemical window, a high ionic conductivity of 0.634 mS cm^-1 at 60 °C and a large Li⁺ transference number of 0.81—remarkably outperforming CNF-COF-free counterparts (0.183 mS^-1 cm and 0.22). As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h at 0.1 mA cm^-2. Impressively, by coupling with LiFePO₄ (LFP) cathodes, the assembled ASS Li battery under 60°C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C with a large capacity retention of ~75 %, surpassing most reported ASS Li batteries using PEO-based electrolytes.